JP2000128979A - Production of polyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound by an effective reaction with little byproducts wherein a specified amount of an alkylene oxide is added to bisphenol A in the presence of a specified amount of water and the water is removed thereafter. SOLUTION: This polyether is obtained by following steps; (A) 2.4-4.0 mol alkylene oxide (e.g. ethylene oxide, propylene oxide, styrene oxide or a long- chain α-olefin oxide) is addition-reacted with one mol bisphenol A in the presence of 5-50 wt.% preferably 10-40 wt.% water and (B) the water in the system is removed. Preferably, then (C) an alkylene oxide is further added. The addition reaction in the above step A is performed under agitation preferably at 30-150 deg.C and at normal pressure to 6.0 kg/cm2 or so for 30 min to 24 h or so. The water removal in the step B is preferably performed by warming under agitation at a reduced pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bisphenol A
To a method for producing a polyether obtained by adding an alkylene oxide to a polyether.

[0002]

2. Description of the Related Art Polyethers obtained by adding alkylene oxides such as ethylene oxide to alcohols and phenols are widely used as nonionic surfactants. In the case of producing a polyether, generally, first, an alcohol as a starting material is charged into a pressurizable reaction tank, then a suitable catalyst is charged, and then, ethylene oxide or the like is supplied and heated and stirred. A method is adopted. When a liquid alcohol such as lauryl alcohol is used as the starting material alcohol, the viscosity of the liquid is low and the reaction can be performed without any special operation. Also, alcohols that are solid at room temperature, such as stearyl alcohol,
Usually, it is liquid at around the reaction temperature (about 80 to 120 ° C.), so that there is no particular difficulty in production.

[0003]

However, when bisphenol A is used as the starting alcohol, the melting point is so high that the polyether is still solid at ordinary reaction temperatures of the polyether, or at best a very viscous liquid. It is.
If the starting alcohol remains solid, the stirring efficiency in the reaction vessel is very poor or cannot be achieved.
For this reason, there is a problem that the number of contacts between the alcohol and the alkylene oxide is small, and the reaction does not proceed sufficiently. This is the same even when the viscosity of the liquid is very high. Bisphenol A, which is a solid at the reaction temperature, is also a compound obtained by adding a few moles of alkylene oxide to itself, and has a low viscosity and fluidity. It is not so difficult operation. However, the addition of the first few moles of alkylene oxide to bisphenol A involves very great difficulties as described above.

A solvent may be used to give the starting material bisphenol A with fluidity, but using a large amount of the solvent reduces the amount of products that can be produced per batch, which is not efficient. In addition, since alkylene oxide has a very high reactivity, it may cause a side reaction with a solvent. For example, if the reaction is continued by using a large amount of water as a solvent, a problem arises in that the alkylene oxide reacts with water to produce a large amount of polyalkylene glycol as a by-product. Accordingly, an object of the present invention is to provide a method for producing a polyether, which is efficient with less by-products.

[0005]

The present inventors have studied a method for efficiently adding alkylene oxide to bisphenol A having such a high melting point as a starting material. By adding a small amount of alkylene oxide in advance in the presence of
The inventors have found that the above-mentioned problems can be solved and completed the present invention.

That is, the present invention relates to a method for producing a polyether by adding an alkylene oxide to bisphenol A. (1) In the presence of 5 to 50% by weight of water based on bisphenol A, based on 1 mole of bisphenol A A process of adding 2.4 to 4.0 moles of an alkylene oxide; (2) a step of removing water present in the system thereafter.

Further, the present invention relates to a method for producing a polyether by adding an alkylene oxide to bisphenol A. (1) In the presence of 5 to 50% by weight of water with respect to bisphenol A, with respect to 1 mol of bisphenol A (2) Then, removing water present in the system; (3) Then, further adding alkylene oxide to the polyether. It is a manufacturing method of.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkylene oxide which is a raw material used in the production method of the present invention include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and long-chain α-olefin oxide. The oxides can be used alone or as a mixture.

In the step (1) of the production method of the present invention, bisphenol A as a starting material is
Water is charged at a rate of 50% by weight. If the charged amount of water is less than 5% by weight, the reaction between the alkylene oxide and bisphenol A does not proceed sufficiently because the fluidity of bisphenol A is not sufficient. If the charged amount of water exceeds 50% by weight, by-products Some polyalkylene glycols only increase. Also, much time and energy are required in the subsequent dehydration step, which is disadvantageous in production. The ratio of water to bisphenol A is more preferably 10 to 40% by weight.

Subsequently, 2.4 to 4.0 moles of an alkylene oxide are added to 1 mole of bisphenol A. This addition reaction proceeds easily because bisphenol A is in a liquid or slurry state having a low viscosity by adding a specific amount of water. Bisphenol A1
When the amount of the alkylene oxide is less than 2.4 moles per mole, the subsequent reaction does not proceed sufficiently because the fluidity of the intermediate obtained by the addition reaction is not sufficient.
Similarly, when the amount is more than 4.0 mol, the alkylene oxide reacts with water in the system to increase by-products.

The conditions for this addition reaction are not particularly limited, but the temperature is preferably about 30 to 150 ° C, more preferably about 80 to 140 ° C. The reaction time depends on the number of moles of the alkylene oxide added, but is usually from 30 minutes to
It is about 24 hours. Reaction pressure is from normal pressure to 6.0 kg / c
m ² .

In the addition reaction of the alkylene oxide, a catalyst may or may not be used. When used, a usual acid catalyst or alkali catalyst that promotes the addition reaction of an alkylene oxide to a hydroxyl group can be used.
For example, alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alcoholate, potassium alcoholate are preferred,
Particularly, an alkali metal hydroxide is preferable. The amount to be used is not particularly limited, but is usually 0.1 to the starting material polyol.
About 1 to 1% by weight is preferable.

In the subsequent step (2), after the addition reaction in the step (1) is completed, water present in the system is removed. The method of removing water is not particularly limited, but a method of removing the water under reduced pressure while heating and stirring is usually preferable. If alkylene oxide is introduced in a subsequent step without sufficiently removing water in this step, a side reaction occurs and polyalkylene oxide is by-produced. The production target product is an alkylene oxide of 2.4 to 4.
When 0 mol is added, the target product is obtained as described above.

When the product to be produced is obtained by adding 4.0 mol or more of alkylene oxide to 1 mol of bisphenol A, after the removal of water in the step (2) is completed, the step (1) is further carried out. An alkylene oxide may be added under similar reaction conditions. In the reaction at this stage, since a small amount of alkylene oxide has already been added to bisphenol A, it becomes a liquid or slurry by heating, and the reaction can be carried out without difficulty by an ordinary method.

According to the production method of the present invention, bisphenol A, which has been difficult to react with an alkylene oxide due to its high melting point, also becomes a liquid or slurry having a low viscosity by adding a specific amount of water. The reaction with the alkylene oxide can be easily performed without causing extra side reactions, and the reaction time can be shortened. Also, since water is removed during the reaction, polyalkylene glycol is hardly produced as a by-product even when an addition reaction of more alkylene oxides is performed.

[0016]

The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified.

Example 1 A 5-liter reaction vessel was charged with 1,140 g (5.0 mol) of bisphenol A, 2.0 g of potassium hydroxide, and 380 g of distilled water.
The mixture was stirred at the same temperature for 1 hour to form a slurry. Thereafter, the temperature was increased to 130 ° C. and ethylene oxide 5
28 g (12 mol) were introduced. After the reaction progressed and the reactor was aged for 30 minutes from the time when the pressure in the reactor became constant, water and volatiles in the system were distilled off by reducing the pressure to 10 mmHg or less. Subsequently, potassium hydroxide as a catalyst was treated with an adsorbent to obtain an ethylene oxide adduct of bisphenol A.

Example 2 A reaction vessel of 10 liters was charged with 1,140 g (5.0 mol) of bisphenol A, 2.0 g of potassium hydroxide, and 380 g of distilled water.
The slurry was kept at 0 ° C. and stirred for 1 hour to form a slurry. Thereafter, the temperature was raised to 130 ° C., and 528 g (12 mol) of ethylene oxide was introduced under pressure. After the reaction progressed and the reactor was aged for 30 minutes from the time when the pressure in the reactor became constant, water and volatiles in the system were distilled off by reducing the pressure to 10 mmHg or less. Subsequently, 1.3 g of potassium hydroxide was added, and 1,672 g (38 mol) of ethylene oxide in the second stage was introduced at 130 ° C. under pressure. After aging for 30 minutes from the time when the reaction progressed and the pressure in the reactor became constant, unreacted ethylene oxide was distilled off under reduced pressure of 10 mmHg or less. Subsequently, potassium hydroxide as a catalyst was treated with an adsorbent to obtain an ethylene oxide adduct of bisphenol A.

Example 3 A 10-liter reaction vessel was charged with 1,140 g (5.0 mol) of bisphenol A, 2.3 g of potassium hydroxide, and 190 g of distilled water.
The slurry was kept at 0 ° C. and stirred for 1 hour to form a slurry. Thereafter, the temperature was raised to 130 ° C., and 696 g (12 mol) of propylene oxide was introduced under pressure. After the reaction progressed and the reactor was aged for 30 minutes from the time when the pressure in the reactor became constant, water and volatiles in the system were distilled off by reducing the pressure to 10 mmHg or less. Subsequently, 1.7 g of sodium hydroxide was added, and 2,204 g (38 mol) of propylene oxide in the second stage was introduced under pressure at 130 ° C. After aging for 30 minutes from the time when the reaction progressed and the pressure in the reactor became constant, unreacted propylene oxide was distilled off under reduced pressure of 10 mmHg or less. Subsequently, sodium hydroxide as a catalyst was treated with an adsorbent to obtain a propylene oxide adduct of bisphenol A.

Example 4 A 10 liter reaction vessel was charged with 1,140 g (5.0 mol) of bisphenol A, 1.8 g of potassium hydroxide, and 190 g of distilled water.
The slurry was kept at 0 ° C. and stirred for 1 hour to form a slurry. Thereafter, the temperature was raised to 130 ° C., and 660 g (15 mol) of ethylene oxide was introduced under pressure. After the reaction progressed and the reactor was aged for 30 minutes from the time when the pressure in the reactor became constant, water and volatiles in the system were distilled off by reducing the pressure to 10 mmHg or less. Subsequently, 3.7 g of sodium hydroxide was added, and 3,740 g (85 mol) of ethylene oxide in the second stage was introduced at 130 ° C. under pressure. After aging for 30 minutes from the time when the reaction progressed and the pressure in the reactor became constant, unreacted ethylene oxide was distilled off under reduced pressure of 10 mmHg or less. Subsequently, sodium hydroxide as a catalyst was treated with an adsorbent to obtain an ethylene oxide adduct of bisphenol A.

Comparative Example 1 A reaction vessel of 10 liters was charged with 1,140 g (5.0 mol) of bisphenol A and 2.0 g of potassium hydroxide, and the temperature was raised to 1 without adding distilled water.
The mixture was kept at 00 ° C. and stirred for 1 hour. Thereafter, the temperature was raised to 130 ° C. to add ethylene oxide under pressure, but the reaction did not proceed because the catalyst was not sufficiently dissolved in bisphenol A.

Comparative Example 2 A 10-liter reaction vessel was charged with 1,140 g (5.0 mol) of bisphenol A, 1.6 g of potassium hydroxide, and 380 g of distilled water.
The slurry was kept at 0 ° C. and stirred for 1 hour to form a slurry. Thereafter, the temperature was raised to 130 ° C., and 440 g (10 mol) of ethylene oxide was introduced under pressure. After aging for another 30 minutes after the pressure in the reactor became constant, 10 m
The pressure was reduced to mHg or less, and water and volatile components in the system were distilled off to obtain a paste-like ethylene oxide adduct. continue,
1.3 g of potassium hydroxide was added, and at 130 ° C. under pressure,
1,672 g (38 mol) of the second stage ethylene oxide was introduced. After aging for 30 minutes after the pressure in the reactor became constant, unreacted ethylene oxide was distilled off under reduced pressure of 10 mmHg or less. Subsequently, potassium hydroxide as a catalyst was treated with an adsorbent to obtain an ethylene oxide adduct of bisphenol A.

Comparative Example 3 A reaction vessel of 10 liters was charged with 1,140 g (5.0 mol) of bisphenol A, 3.3 g of potassium hydroxide, and 380 g of distilled water.
The slurry was kept at 0 ° C. and stirred for 1 hour to form a slurry. Thereafter, the temperature was raised to 130 ° C., and 2,200 g (50 mol) of ethylene oxide was introduced under pressure. The reaction proceeds,
After aging for another 30 minutes from the time when the pressure in the reactor became constant, water and volatile components in the system were distilled off by reducing the pressure to 10 mmHg or less. Subsequently, potassium hydroxide as a catalyst was treated with an adsorbent to obtain an ethylene oxide adduct of bisphenol A.

With respect to the products obtained in the above Examples and Comparative Examples, the number of moles of alkylene oxide added to the reactants of the first and second stages, the fluidity of the reactants of the first stage, and the by-products formed Are shown in Tables 1 and 2. The amount of by-product was analyzed by GPC.

[0025]

[Table 1]

[0026]

[Table 2]

* The number of moles added per mole of bisphenol A. The molecular weight of the by-product was about 100-200. As is clear from the above results, when an alkylene oxide was added to bisphenol A in the production method of the present invention,
Since the fluidity at the completion of the first-stage reaction was better than that of Comparative Example 2, the subsequent addition proceeded smoothly.
Further, the amount of by-products could be suppressed to a small amount as compared with the case where dehydration was not performed on the way as in Comparative Example 3. In Comparative Example 1, although the first-stage addition reaction of ethylene oxide was performed without adding water, the addition reaction did not proceed.

[0028]

The effect of the present invention is to provide a method for producing a polyether obtained by adding an alkylene oxide to bisphenol A, which can be produced efficiently with little by-products.

Claims (2)

[Claims] 1. A method for producing a polyether by adding an alkylene oxide to bisphenol A, comprising the steps of: (1) adding alkylene oxide to 1 mol of bisphenol A in the presence of 5 to 50% by weight of water based on bisphenol A; (2) a step of removing water present in the system after the addition of 2.4 to 4.0 mol; 2. A method for producing a polyether by adding an alkylene oxide to bisphenol A, comprising the steps of: (1) adding alkylene oxide to 1 mol of bisphenol A in the presence of 5 to 50% by weight of water based on bisphenol A; (2) a step of removing water present in the system; and (3) a step of further adding an alkylene oxide.